JP4504120B2 - Method for forming a paint coating film to develop uneven shape on the surface - Google Patents

Description

  The present invention relates to a paint and a seal capable of expressing with excellent design by utilizing a phenomenon in which a concavo-convex pattern appears on the surface of a coating film in the process of forming a coating film by evaporating the solvent of the polyvinyl butyral resin solution.

Traditionally, Illastend (trademark Harako Chemical Industry Co., Ltd.) as a paint that can be directly colored on glass, acrylic, PVC plates, metal plates, ceramics, etc. Glass Deco (trademark Yamato Co., Ltd.) and the like exist as paints to be made.
Although not commercialized, there is a proposal for a paint for stained glass (Patent Document 1) in which a pigment does not elute even when immersed in warm water using an acrylate resin emulsion as a main raw material.
However, these paints have a uniform and almost smooth surface even when the resin is cured to form a coating film, which is interesting for elementary school children and infants, but has a profound feeling and handwriting feeling for the general public. It was poor.
Although it can be applied thickly, it is not uniformly applied and color unevenness is likely to occur, and since the surface of the color unevenness is only smooth, there remain defects such as poor expressiveness.
JP-A-6-172681

  Therefore, as a result of diligent research on this, the present inventors have found that when a specific type of plasticizer is mixed with a butyral resin having a certain range of butyralization degree, an uneven shape is expressed on the surface, Using these characteristics, we have succeeded in developing paints and seals with excellent design.

In order to solve the above-mentioned problems, the method for forming a paint film for developing a concavo-convex shape on the surface according to claim 1 comprises (1) polyvinyl butyral having a butyralization degree of 50 to 85 mol% as a main component, and (2) the polyvinyl (4) The molecular weight of butyral is in the range of 200 to 2500 in terms of average polymerization degree, and (3) a plasticizer having an ester bond is mixed in the range of 25 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl butyral, A paint composition is prepared by mixing a solvent so that the total weight of the polyvinyl butyral added with a plasticizer is in the range of 5 wt% to 20 wt%, and the paint composition is applied to the surface of the target substrate. It is characterized in that it is coated and dried at room temperature and in an open system environment so that a concavo-convex shape is developed on the surface of the coating film.
The invention described in claim 2 is characterized in that, in the above invention, the degree of butyralization of polyvinyl butyral is 60 to 75 mol%.
The invention described in claim 3 is characterized in that in the above invention, the average degree of polymerization of the polyvinyl butyral molecular weight is 600-2000.
The invention described in claim 4 is characterized in that, in the above invention, the plasticizer is a triethylene glycol plasticizer.
The invention according to claim 5 is characterized in that, in the above invention, the solvent is an alcohol solvent.

  The paint and seal of the present invention can form a colored coating film with excellent translucency on the surface of glass such as stained glass, plastic, metal, ceramics, etc. A crepe-like or crepe-like pattern is expressed, so that a solid feeling and a handwriting feeling can be expressed, and an expression that is rich in expressiveness and excellent in design is possible.

  At that time, depending on the molecular weight of the butyral resin, the choice of plasticizer and the type of solvent, etc., it is possible to change the size of the uneven shape, the presence or absence of gloss, etc., and as a result, the size, gloss, gloss, etc. of the uneven shape It is possible to express subtle changes in color and texture.

  In addition, sticking with a seal is possible in the formation of a coating, and the seal mainly composed of butyral resin has a hydrophobic part and a hydrophilic part, so it maintains an appropriate contact with the target substrate. And since it is not strong adhesion | attachment, releasability can also be ensured and it can have the balance of adhesiveness and peelability.

  Furthermore, by using alcohols as the solvent that evaporates during the formation of the coating film, it is possible to provide paints and seals that are environmentally friendly and have no fear of sick house syndrome or the like.

The resin that is the main component of the paint and seal of the present invention is a butyral resin.
The butyral resin refers to polyvinyl butyral and is a resin having the following chemical structural formula.

X = Vinyl acetate component Y = Vinyl alcohol component Z = Vinyl butyral component That is, polyvinyl butyral is a vinyl acetate component having a property intermediate between a vinyl alcohol component serving as a hydrophilic portion and a vinyl butyral component serving as a hydrophobic portion. To form a copolymer. Among them, the ratio of the hydrophilic part and the hydrophobic part is determined as the degree of butyralization, but the present inventors, as will be described in detail later, have a butyral resin having a certain range of butyralization degree. It has been found that when a specific type of plasticizer is mixed, an uneven shape appears on the surface.
Therefore, first, the following test was conducted to investigate the relationship between the degree of butyralization and the development of the uneven shape.
The results are shown in Table 1.
According to Table 1, although there are differences in conditions such as the number average molecular weight and the PVB weight ratio, it has been found that in the range of the butyral degree of 50 to 85 mol%, there is a possibility of expression of an appropriate uneven shape in the butyral resin. . In the table, the triethylene glycol plasticizer refers to tri (ethylene glycol) bis (2-ethylhexanoate).

Subsequently, in the butyral resin having the above-mentioned butyralization degree of 80 to 85 mol%, the influence of the molecular weight on the expression of the uneven shape was examined.
The mixture of the plasticizer mentioned later was made into the fixed ratio, and the relationship between the average degree of polymerization of butyral resin and ethanol solution density | concentration was tested in it.
The results are shown in Table 2.
As a result, although there is a relationship with the concentration of the ethanol solution, there is a possibility that the uneven shape is expressed between the average degree of polymerization of 700 to 2400, and particularly the appearance of the uneven shape excellent in the vicinity of the average degree of polymerization of 700 to 2000 is observed. It was seen.

Next, an attempt was made to add a plasticizer to the butyral resin. That is, as described above, butyral resin is a resin in which functional groups opposite to each other exist in the hydrophilic part and the hydrophobic part, but the resin is unevenly distributed in either the hydrophilic part or the hydrophobic part. Attention has been focused on plasticizers having an ester bond as plasticizers that act on the surface, particularly plasticizers that act on the hydrophilic portion. An attempt was made to make softening of the butyral resin unevenly distributed by unilaterally acting a plasticizer on the hydrophilic portion.
As the plasticizer having an ester bond, a triethylene glycol type was typified, and an appearance test of the uneven shape was performed.
The results were as shown in Table 3.
First, a butyral resin having a butyralization degree of 79 mol% is selected, and an ethanol solution is prepared by adding tri (ethylene glycol) bis (2-ethylhexanoate) to the butyral resin. The mixing ratio of the plasticizer to the butyral resin is changed. Then, the presence or absence of the appearance of irregularities was observed.
As a result, with respect to the butyral resin, it was difficult for the plasticizer to exhibit unevenness when the plasticizer was 90:10 or less. However, a large shape was observed in the range of 80:20 to 70:30, and many small irregularities appeared at 60:40, and an excellent irregular shape was confirmed.

Subsequently, since the effectiveness of the triethylene glycol plasticizer was confirmed, the following tests were conducted in order to widely examine the types of plasticizers.
From the types of plasticizers, phthalic acid, adipic acid, and castor oil were selected, and the following tests were conducted.
As a result, in addition to the triethylene glycol type with large unevenness and strong gloss, the matte tone with large unevenness and less gloss is found in the phthalic acid type and adipic acid type, and the castor oil has a small uneven shape and glossy appearance. As a result, it was confirmed that the most uneven plasticizer having an ester bond exhibited an uneven shape.
Therefore, by selecting the type from among plasticizers having an ester bond, it becomes possible to adapt to the design taste.

Furthermore, a test was conducted to examine the relationship between the uneven shape of plasticizers having different types and average polymerization degrees of the butyral resin.
It is Table 5.
As a result, when a triethylene glycol plasticizer was used, small irregularities were obtained at a low degree of polymerization and large irregularities were obtained at a high degree of polymerization. When relatively cheap castor oil was used, small irregularities were obtained at a low polymerization degree, and large irregularities were obtained at a high polymerization degree. However, when the degree of polymerization is high, the triethylene glycol plasticizer is glossy, whereas the castor oil is not glossy. Therefore, the presence or absence of gloss can be selected according to the purpose.

Furthermore, with respect to the butyral resin in which the plasticizer was mixed, a solvent to be dissolved was tested for its influence on the uneven shape expression.
The results are shown in Table 6.
As a result, at 700 where the average degree of polymerization is low, small irregularities appear weak in the ethanol solution and strong in mixed ethanol and isopropyl alcohol, whereas in 2000 where the average degree of polymerization is high, ethanol has small irregularities and the mixed ethanol and With isopropyl alcohol, large irregularities were strongly expressed.
Depending on the type of solvent and the degree of polymerization of the butyral resin, it was found that the shape of the uneven shape was changed.Therefore, by selecting the type of solvent and the degree of polymerization of the butyral resin, different forms were obtained. An uneven shape can be obtained.

Polyethylene butyral (PVB) having an average polymerization degree of 700 is mixed with triethylene glycol-based plasticizer, tri (ethylene glycol) bis (2-ethylhexanoate) as a plasticizer at a ratio of 70:30 wt%, and an ethanol solvent is used. A black paint was prepared by adding a pigment carbon black of 4 wt% to a 15 wt% solution.
The black paint was applied on a glass substrate and waited for drying.
The uneven shape of the paint of the present invention is a size that can be visually observed, and adds a change and taste to the design tone, but in order to observe its physical form, it is photographed with a CCD camera with about 2.11 million pixels. did.
FIG. 3 shows an enlarged photograph with a magnification of 100. According to this photograph, a convex crest is formed on the periphery of a diameter of about 100 μm to 300 μm, and a concave trough is formed therein. Irregular patterns were observed.

Although the exact theory has not yet been obtained as to the mechanism by which this uneven shape is expressed, the inventors presume that it is as follows.
The butyral resin forms a copolymer of a vinyl alcohol component serving as a hydrophilic part, a vinyl butyral component serving as a hydrophobic part, and a vinyl acetate component having intermediate properties, and the butyral resin has an ester bond. When a plasticizer is mixed, an ester bond having a —COO— group exhibits affinity for an alcohol component having an OH group, while one vinyl butyral group is a hydrophobic group and does not exhibit affinity.
Therefore, even if the softening of the resin is attempted by mixing the plasticizer, the whole does not soften uniformly, but acts more on the part having the hydrophilic part, acts less on the hydrophobic part, and acts on the intermediate part. It performs an intermediate action, and as a result, the degree of softening is biased depending on the site.
Then, a solvent, a pigment, a dye, and the like are added to the paint to complete the paint. When this is applied, in the drying process, first, transpiration starts from a solvent having a low volatilization temperature in the mixed components (FIG. 4 (1)). (See (2)).
The solvent is a butyral resin that is biased in the resin part softened by the mixing of the plasticizer, and exhibits a dissolving action at a site where there are many softened parts, but not so much at other parts. Bias occurs.
And, naturally, the solvent starts to evaporate at the site where more solvent is present, but the temperature of the surrounding area decreases due to the latent heat absorption of the vapor accompanying the volatilization, and when the temperature approaches the glass transition temperature of the plasticized butyral resin, the phase transition occurs. The low-temperature solute part hardens and sticking preferentially begins. The adhering portion becomes a recess relatively, and valley formation proceeds (see FIG. 4 (3)).
When the bottom of the trough is fixed, the solvent is volatilized and the surrounding solution has a vector acting in the direction of discharging from the bottom of the trough center to the four sides, and conversely, the periphery has a hydrophobic part with little softening. Resin is accumulated here (see FIG. 4 (4)).
In this way, a wall is formed between the valley and the mountain that covers the periphery, that is, an uneven shape is formed (see FIG. 4 (5)).

The case where the paint of the present invention as obtained in Example 1 is drawn using, for example, a stained glass as shown in FIG. 5 as a substrate will be described. First, a composition is drawn on a glass substrate and there are, for example, 12 colors of the paint of the present invention. Prepare the alignment and color the composition.
At this time, the presence or absence of gloss and the size of the unevenness are selected from those prepared according to the type of solvent, the degree of polymerization of the butyral resin, and the type of plasticizer.
Then, when waiting for the drying, an uneven shape appears in the part drawn along the composition through the process described in the above mechanism, which induces a profound feeling, a handwriting feeling, etc., as shown in FIG. Stained glass with unique design characteristics.

(Example of creating a seal)
Polyethanol butyral (PVB) having an average polymerization degree of 2000 is mixed with triethylene glycol plasticizer, tri (ethylene glycol) bis (2-ethylhexanoate), as a plasticizer at a ratio of 70:30 wt%, and mixed ethanol IP A 12 wt% solution was prepared with a solvent to prepare a base solution for sealing.
30 mL of the substrate solution for sealing was uniformly cast on the bottom of a glass petri dish having a diameter of 120 mm, and was dried in an open system overnight at room temperature.
After confirming the formation of the coating film, a cut was made along the outer periphery of the petri dish with a cutter, a gap was made in a part as if wrinkled, and the whole petri dish was immersed in a water bath filled with cold water for 3 minutes.
Taking advantage of the property of being stiffened in water and becoming harder and less adhesive to glass, the colorless and transparent seal formed on the bottom of the petri dish body is slowly and carefully peeled off in water, and a plastic plate made of polypropylene. It was flattened and pasted.
After wiping off the moisture on the seal surface with blotting paper, use the pigmented pigment of the present invention to paint on the seal surface, and if necessary, use the seal substrate solution as a paste to paint The topping of decorative articles (star-shaped beads) was performed.
Furthermore, as an application example, when preparing the present paint containing the base solution for sealing or the pigment, an appropriate amount of aroma such as aroma oil was added to create a scented seal.
As a result, a circular seal having a diameter of 120 mm and a thickness of about 100 μm was completed. When this was affixed to the rear window of a passenger car from the inside, the fabric was transparent, the pictured part was translucent, and the uneven surface looked shining with sunlight or light up at night, giving it an excellent decoration. . Furthermore, it was excellent in weather resistance and durability.

  The paints and seals of the present invention are widely used as paints and seals for stained glass, as paints and seals drawn on the surface of glass, synthetic resin, plywood, tile, metal, ceramics, and as paints and seals for nail art. Application is possible.

The front photograph in the state where small unevenness of 1 mm or less in diameter was developed with the paint of the present invention. The front photograph of the present invention paint in a state where large irregularities with a diameter of 2 to 3 mm are developed. A front view photograph of the uneven shape of the paint of the present invention, taken with a CCD camera of 2.11 million pixels of about 100 times, and further magnified at a magnification of 100 times. It is a schematic diagram which shows the process until the uneven | corrugated shape is formed in the drying after application | coating this invention paint, Comprising: (1) is the state immediately after application | coating, and (2) begins to evaporate from the solvent with low volatilization temperature. In the state where (3) is fixed to the low-temperature solute part after the phase transition and becomes a depression and a valley is formed, (4) is a hydrophobic part with little softening left at the periphery. A state in which the resin component is accumulated, (5) shows a state in which a wall is formed between the valley and the mountain that covers the periphery, and the uneven shape is completed. The front photograph which drew the paint of this invention on the glass substrate and made it stained glass.

Claims (5)

(1) A polyvinyl butyral having a butyralization degree of 50 to 85 mol% as a main component,

(2) The molecular weight of the polyvinyl butyral is in the range of 200 to 2500 in terms of average polymerization degree,
(3) A plasticizer having an ester bond is mixed in a range of 25 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl butyral,
(4) adjusting a paint composition obtained by mixing a solvent so that the total weight of the polyvinyl butyral added with a plasticizer is in the range of 5 wt% to 20 wt% ;
Casting and coating the paint composition on the surface of the target substrate,
A method for forming a paint film, which comprises drying the surface at room temperature and in an open environment to develop a concavo-convex shape on the surface.
The method for forming a paint film according to claim 1, wherein the degree of butyralization of polyvinyl butyral is 60 to 75 mol%.
The method for forming a paint coating film according to claim 1 or 2, wherein the average degree of polymerization of the polyvinyl butyral molecular weight is 600 to 2,000 . The method for forming a paint coating film according to any one of claims 1 to 3, wherein the plasticizer is a triethylene glycol plasticizer . The method for forming a paint coating film according to any one of claims 1 to 4, wherein the solvent is an alcohol solvent .